scholarly journals THE REACTIONS OF ACTIVE NITROGEN WITH HYDROGEN SULPHIDE AND CARBON DISULPHIDE

1960 ◽  
Vol 38 (3) ◽  
pp. 334-342 ◽  
Author(s):  
R. A. Westbury ◽  
C. A. Winkler
Keyword(s):  
Nitrogen Atom ◽  
Hydrogen Sulphide ◽  
Temperature Effects ◽  
Carbon Disulphide ◽  
Third Body ◽  
Active Nitrogen

The destruction of either hydrogen sulphide or carbon disulphide by active nitrogen appears to be minimal at some temperature in the range 200–250 °C. Both reactions yield large amounts of polymer.It is postulated that the main reactions involve destruction of the reactant as it acts as a third body for recombination of nitrogen atoms. As the temperature is increased, dissociation of the nitrogen atom – reactant complex apparently increases. To account for the observed temperature effects, it is assumed that reactions also occur to regenerate reactant.

THE REACTION OF ACTIVE NITROGEN WITH PROPYLENE

1952 ◽  
Vol 30 (12) ◽  
pp. 915-921 ◽  
Author(s):  
G. S. Trick ◽  
C. A. Winkler
Keyword(s):  
Double Bond ◽  
Nitrogen Atom ◽  
Hydrogen Cyanide ◽  
Atomic Hydrogen ◽  
Atomic Nitrogen ◽  
Active Nitrogen

The reaction of nitrogen atoms with propylene has been found to produce hydrogen cyanide and ethylene as the main products, together with smaller amounts of ethane and propane and traces of acetylene and of a C4 fraction. With excess propylene, the nitrogen atoms were completely consumed and for the reaction at 242 °C., 0.77 mole of ethylene was produced for each mole of excess propylene added. For reactions at lower temperatures, less ethylene was produced. The proposed mechanism involves formation of a complex between the nitrogen atom and the double bond of propylene, followed by decomposition to ethylene, hydrogen cyanide, and atomic hydrogen. The ethylene would then react with atomic nitrogen in a similar manner.

Pyrimidine reactions. VIII. Methiodides formed from some dimethylaminopyrimidines

1965 ◽  
Vol 18 (2) ◽  
pp. 199 ◽  
Author(s):  
DJ Brown ◽  
T Teitei
Keyword(s):  
Nitrogen Atom ◽  
Methyl Iodide ◽  
Hydrogen Sulphide ◽  
Aqueous Ethanol ◽  
Alkaline Degradation ◽  
Dimethylamino Group ◽  
Nucleoside Synthesis ◽  
Sodium Hydrogen ◽  
Quaternary Compounds

4.Dimethylaminopyrimidine and its 2-chloro-, 2-dimethylamino-, 6-chloro-, 6-methylthio-, and 6-dimethylamino-derivatives are quaternized by methyl iodide at N 1. The structures of the resulting methiodides are proven by alkaline degradation to known oxopyrimidines. 4-Dimethylamino-2-(and 6-)methoxypyrimidine and 2-dimethylamino-4-methoxypyrimidine all undergo quaternization on a nuclear nitrogen atom followed by spontaneous loss of methyl iodide to yield oxopyrimidines (cf. the so-called Johnson and Hilbert nucleoside synthesis). The unique lability of the dimethylamino group in these quaternary compounds is exemplified in the con- version of 2-dimethylamino-1,6-dihydro-1,3-dimethyl-6-oxopyrimidinium iodide into 1,3-dimethyluracil by mere dissolution in water or aqueous ethanol, and by the reaction of 2,4-bisdimethylamino-I-methylpyrimidinium iodide with ethanolic sodium hydrogen sulphide to give 4-dimethylamino-1,2-dihydro-1-methyl-2-thio- pyrimidine.

THE REACTIONS OF ACTIVE NITROGEN WITH THE BUTANES

1954 ◽  
Vol 32 (7) ◽  
pp. 718-724 ◽  
Author(s):  
R. A. Back ◽  
C. A. Winkler
Keyword(s):  
Nitrogen Atom ◽  
Rate Constants ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Activation Energies ◽  
Reactive Species ◽  
Atomic Nitrogen ◽  
Initial Attack ◽  
Active Nitrogen ◽  
Rate Controlling Step

The main product of the reactions of active nitrogen with n- and iso-butanes at 75 °C. and 250 °C. was hydrogen cyanide. Small amounts of C2 hydrocarbons, mainly ethylene and acetylene, were produced in both reactions. Second order rate constants were calculated on the assumption that the reactive species in active nitrogen is atomic nitrogen, and that the initial attack of a nitrogen atom is the rate-controlling step. The activation energies were then estimated to be 3.6 kcal. and 3.1 kcal. and the probability factors 4.5 × 10−4 and 4.4 × 10−4, for the n-butane and isobutane reactions respectively.

PYROLYSIS OF ETHYL MERCAPTAN

1955 ◽  
Vol 33 (8) ◽  
pp. 1281-1285 ◽  
Author(s):  
Jean L. Boivin ◽  
Roderick MacDonald
Keyword(s):  
Hydrogen Sulphide ◽  
Carbon Disulphide ◽  
Optimum Temperature ◽  
Mass Spectral Analysis ◽  
Mass Spectral ◽  
Ethyl Mercaptan ◽  
Catalyst Metal ◽  
Free Sulphur ◽  
Carbonyl Sulphide ◽  
By Products

The decomposition of ethyl mercaptan to ethylene and hydrogen sulphide was studied at various temperatures, with and without a catalyst. Metal sulphides (copper, nickel, and cadmium) proved to be the most efficient catalysts for cracking ethyl mercaptan into unsaturated end products, the optimum temperature being 500–600 °C. When no catalyst was used a 40–50% yield of ethylene and a nearly quantitative conversion to hydrogen sulphide was observed between 600 and 700 °C. Other products identified in the exit gas were carbon disulphide, carbonyl sulphide, methane, hydrogen, ethane, thiophene, diethyl sulphide, and free sulphur. Identification of these products was aided by infrared and mass spectral analysis of the gas. A tentative mechanism for the reaction justifying the presence of the above by-products is outlined.

THE REACTION OF NITROGEN ATOMS WITH OXYGEN ATOMS IN THE ABSENCE OF OXYGEN MOLECULES

1961 ◽  
Vol 39 (8) ◽  
pp. 1601-1607 ◽  
Author(s):  
C. Mavroyannis ◽  
C. A. Winkler
Keyword(s):  
Nitric Oxide ◽  
Nitrogen Atom ◽  
Rate Constant ◽  
Rate Constants ◽  
Flow System ◽  
Titration Method ◽  
Active Nitrogen ◽  
Reaction Tube ◽  
Fast Flow ◽  
Oxygen Atoms

The reaction has been studied in a fast-flow system by introducing nitric oxide in the gas stream with excess active nitrogen. The nitrogen atom consumption was determined by titrating active nitrogen with nitric oxide at different positions along the reaction tube. The rate constant is found to be k1 = 1.83(± 0.2) × 1015 cc2 mole−2 sec−1 at pressures of 3, 3.5, and 4 mm, and with an unheated reaction tube.The homogeneous and surface decay of nitrogen atoms involved in the above system were studied using the nitric oxide titration method, and the rate constants were found to be k3 = 1.04 ± 0.17 × 1016 cc2 mole−2 sec−1, and k4 = 2.5 ± 0.2 sec−1 (γ = 7.5 ± 0.6 × 10–5), respectively, over the range of pressures from 0.5 to 4 mm with an unheated reaction tube.

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